CA2206583A1 - Process for producing sponge iron and plant for carrying out the process - Google Patents
Process for producing sponge iron and plant for carrying out the processInfo
- Publication number
- CA2206583A1 CA2206583A1 CA002206583A CA2206583A CA2206583A1 CA 2206583 A1 CA2206583 A1 CA 2206583A1 CA 002206583 A CA002206583 A CA 002206583A CA 2206583 A CA2206583 A CA 2206583A CA 2206583 A1 CA2206583 A1 CA 2206583A1
- Authority
- CA
- Canada
- Prior art keywords
- gas
- offgas
- duct
- reduction
- purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 192
- 239000000463 material Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims description 39
- 238000000746 purification Methods 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 229960005191 ferric oxide Drugs 0.000 claims description 12
- 235000013980 iron oxide Nutrition 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000779 smoke Substances 0.000 claims description 11
- 239000000567 combustion gas Substances 0.000 claims description 10
- 239000000969 carrier Substances 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 6
- 229910000805 Pig iron Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000011946 reduction process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 6
- 238000005201 scrubbing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GWUSZQUVEVMBPI-UHFFFAOYSA-N nimetazepam Chemical compound N=1CC(=O)N(C)C2=CC=C([N+]([O-])=O)C=C2C=1C1=CC=CC=C1 GWUSZQUVEVMBPI-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
- C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
- C21B2100/64—Controlling the physical properties of the gas, e.g. pressure or temperature
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
- C21B2100/66—Heat exchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Manufacture Of Iron (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Hydroponics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
In a process for producing sponge iron from particulate iron oxide-containing material, iron oxide-containing material is reduced to sponge iron with a reducing gas in a reduction zone (4) and gas produced during reduction is withdrawn as top gas. In order to effectively use top gas produced during ore reduction, the CO2 contained in the top gas is removed, the thus obtained CO2containing waste gas is mixed with an oxygen-containing waste gas is mixed with an oxygen-containing gas, is burned and the thermal energy thus produced is supplied to a consumer.
Description
CA 02206~83 1997-0~-30 The invention relates to a process for producing sponge iron from particulate iron-oxide-containing material, wherein the iron-oxide-containing material in a reduction zone is reduced to sponge iron by means of reducing gas and the gas forming during reduction is withdrawn as top gas, as well ~s to a plant for carrying out the process.
With a process of this type known, for instance, from EP-B - O 010 627, from DE-C -40 37 977 and from AT-B - 376,241, the sponge iron formed by the direct reduction is smelted in a meltdown gasifying zone under supply of lumpy carbon carriers and oxygen-cont~ining gas, wherein a fluidized bed is formed in the meltdown gasifying zone from the lumpy carbon carriers and by blowing in oxygen-cont~inin~ gas, in which fl~ li7eci bed the sponge iron particles top-charged into the meltdown gasifiying zone are braked and melted. In doing so, a reducing gas containing CO and H2 is produced, which is injected into the reduction zone and reacted there.
During this reaction, a large amount of top gas incurs, which still has a considerable content of carbon monoxide and hydrogen. If utilization of this top gas is feasible in an economic manner, production costs for sponge iron and pig iron melted therefrom or steel pre-products produced therefrom will be very low.
It is known (DE-C - 40 37 977) to supply top gas escaping from the reduction zone to a further reduction zone for reducing additional iron-oxide-containing m~teri~l after having been subjected to pllrif~ tion~ The treatment of top gas, in general, is effected by initially purifying the same from solids particles in a scrubber while being strongly cooled. After this, the C02 contained in the top gas is elimin~ted, because this would impede further utilization of the top gas as a reducing gas. Various methods have been known for the purification of top gas from C02, for instance, the pressure-swing process or chemical C02-scrubbing.
According to DE-C - 40 37 977, it has been possible to utilize the energy chemically bound in the top gas to a major extent. Yet, this involves the problem of C02-containing offgas incurring in the purification of top gas, which offgas has to be disposed of in an environmentally safe manner.
This offgas, i.a., contains CO, H2, CH4 as well as H2S and, as a result, cannot be released to the environment in such state for reasons of environmental protection. For this reason, it is suited for further processing also to a limited degree only. Consequently, the sulfur compounds usually are elimin~ted from the offgas. So far, such desulfurization has been carried out by means of various methods, such as, for instance, by what is called "Strefford scrubbing"
or by catalytic oxidation on activated carbon, etc. From DE-B - 37 16 511 it is known to remove H2S from C02-containing offgas in a desulfurization reactor by aid of sponge iron. All of these methods are expensive, requiring additional materials, such as activated carbon or absorbants, which, i.a., must be stored and disposed of separately.
It is internally known to bleed off C02-con~:~ining offgas. However, such bleeding off involves the provision of combustible supporting gas as ignition and carburizing gas, since the calorific value of the C02-cont~inin~ offgas is only low.
CA 02206~83 1997-0~-30 From EP-A - O 571 358 it is known to subject top gas incurring in the direct reduction of fine ore by aid of a reducing gas formed of reformed natural gas to C02-scrubbing and to admix the thus purified top gas to fresh reducing gas obtained from natural gas by reforming and to introduce this gas mixture into the reduction zone. Again, this involves the problem of disposing of the C02-containing offgas incurring in the purification of the top gas, although this offgas, due to the production of the reducing gas from reformed natural gas, has a lower H2S-content than the offgas incurring in the top-gas purification of reducing gas obtained from lumpy carbon carriers.
The invention aims at avoiding these disadvantages and difficulties and has as its object to provide for an efficient way of uitlization of the top gas incurring in the reduction of ore, such as a direction reduction for producing sponge iron, by overcoming the difficulties involved in the prior art. In particular, CC~2-containing offgas not only is to be processed and disposed of in an environmentally safe manner, but also is to be utilized energetically to the highest degree possible. Furthermore, problems involved in the separation of H2S, which takes place simnlt~neously with the separation of C02, likewise are to be solved in anenvironmentally safe manner.
In accordance with the invention, this object is achieved with a process of the initially defined kind by the combination of the following measures:
~ that the top gas is subjected to C02 purification, ~ that C02-cont~ining offgas separated in C~2 purification is mixed with an oxygen-containing gas and is burnt, and that its thermal energy is supplied to a consumer.
According to the invention, it is feasible to completely utilize the caloric content of the C02-containing offgas even though its energy content is not very high, without thereby affecting the environment.
Preferably, the C02-cont~ining offgas is burnt at least partially while indirectly giving off heat to reducing gas, ~ whereupon particulate iron-o~ide-containing material is reduced by means of the heated reducmg gas.
A particular advantage of the invention is to be seen in that the C02-cont~ining offgas separated from the top gas of a reduction process at least for the major part again is energetically beneficial to a reduction process, which reduction process may be a reduction process in addition to the reduction process forming the top gas or is identical with the same, which means that at least a portion of the top gas purified from C02 may be recycled as a reducing gas or an admixture to the reducing gas, to the reduction process in which it has incurred as top gas (which is known, for instance, from DE-B - 37 16 511).
-CA 02206~83 1997-0~-30 According to a preferred embodiment, the C02-containing offgas separated in C02 purifi~tion additionally is mixed with a combustible gas.
Preferably, at least a portion of the top gas forming in a reduction, such as a direct reduction, of particulate iron-oxide-containing material by means of reducing gas is employed as a combustible gas. Thereby, it is feasible to ensure heating up of the reducing gas to reduction temperature without using a foreign gas (except for the supply of an 02-cont~ining gas, such as air).
Preferably, the top gas subjected to C~2 purification is formed in a first reduction zone and the top gas purified from C02, after heating, is used as a reducing gas in at least one further reduction zone for reducing further particulate iron-oxide-cont~ining material, being reacted there. Due to these measures, it is possible to utilize the reducing gas formed in a large amount from lumpy carbon carriers in a meltdown gasifying zone, for the production of amounts of sponge iron as large as possible to an optimum degree after reaction in the reduction zone, after which it still has a considerable content of carbon monoxide and hydrogen.
In doing so, top gas formed in the second reduction zone suitably at least partially is admixed as a combustible gas to C02-containing offgas separated in C02 purification and is burnt while indirectly giving off heat to the reducing gas fed to the second reduction zone.
Advantageously, the reduction or elimin~tion of C02 is effected by means of the pressure swing adsorption process. This process is particularly advantageous if top gas having only a slight pressure incurs, because the vapor consumption for chemical scrubbing will increase enorrnously at a low pressure. When producing reducing gas from reforrned natural gas, chemical scrubbing is recommended for C02 removal.
Preferably, sponge iron from the first reduction zone is smelted in a meltdown gasifying zone while supplying solid carbon carriers and oxygen-cont~ining gas, thus forming a CO- and H2-containing reducing gas to be injected into the first reduction zone and reacted there.
A plant for carrying out the process, which comprises a reduction shaft furnace for particulate iron-oxide containing material including a supply duct for reducing gas as well as a discharge duct for top gas, is characterized in that the top-gas discharge duct runs into a C02 purification means, from which a reducing-gas supply duct departs, conducting the C02-purified top gas to a reduction shaft furnace via a heating means for the C02-purified top gas, and that an offgas duct departs from the C~2 purification means, leading separated C02-cont~ining offgas to a heating means, a duct conducting an oxygen-containing gas to the heating means running into the offgas duct.
A preferred embodiment is characterized in that an offgas duct departs from the C02 purification means, conducting separated C02-containing offgas at least partially to a heating means, a combustion-gas duct conducting a combustible gas to the heating means running into the offgas duct.
CA 02206~83 1997-0~-30 To utilize for the reduction process the energy contained in the C02-containing offgas, the heating means into which the offgas duct conducting the C02-containing offgas runs advantageously is designed as an indirect heating means for heating CO2-purified top gas, the reducing-gas supply duct conducting this top gas running into the heating means.In order to render feasible the combustion of the C02-con~ining offgas without any foreign gas, the combustion-gas duct suitably departs from a reduction shaft furnace, at least partially receiving the top gas incurring in the reduction shaft furnace.
According to a preferred embodiment, two reductioll shaft furnaces are provided,which are flow-connected via the top-gas discharge duct of the first reduction shaft furnace, via the C~2 purification means and via the reducing-gas supply duct departing therefrom and leading through the heating means.
In this case, the combustion-gas duct suitably departs from the second reduction shaft furnace.
A preferred embodiment is characterized by a melter gasifier, into which a conveying duct conveying the sponge iron from the first reduction shaft furnace runs and which comprises supply ducts for oxygen-containing gases and for solid carbon carriers as well as taps for pig iron and slag and from which a supply duct for reducing gas formed in the melter gasifier departs, running into the first reduction shaft furnace.
Preferably, the gas purification means is designed as a pressure swing adsorption plant.
Suitably, an offgas duct carrying off separated C02-containing offgas runs into a heating means designed as a steam generator.
Preferably, an offgas duct carrying off separated C02-containing offgas runs into a heating means the smoke gases of which may be carried off via a smoke-gas discharge duct comprising a heat exchanger, wherein material to be heated, such as coal, ore, etc., may be directly contacted with the smoke gas in the heat exchanger.
Another preferred embodiment is characterized in that an an offgas duct carrying off separated C02-containing offgas is conducted via a heat exchanger provided in the top-gas discharge duct of a reduction shaft furnace and subsequently runs into a heating means.
In the following, the invention will be explained in more detail by way of several processes each illustrated in a block diagram in Figs. 1 to 3.
According to Figs. 1 to 3, particulate iron-oxide material, preferably lumpy iron ore, and possible fluxes are supplied to a first reduction shaft furnace 1 through a duct 2 in a known manner. Reducing gas is blown into the reduction shaft furnace through a supply duct 3, ascending in counter-flow to the descending iron ore and effecting the reduction of the charge in t'ne reduction zone 4. After having streamed through the shaft furnace 1, this gas is carried off as a top gas via a top-gas discharge duct 5.
The reduced burden, which contains iron in the form of sponge iron, gets into a melter gasifier 7 via conveying ducts preferably designed as downpipes 6. Via a duct 8, a lumpy carbon carrier, for instance, in the form of brown-coal high-temperature coke, as well as, if CA 02206~83 1997-0~-30 desired, coal, and, in addition, via a duct 9 an oxygeh-containing gas, are supplied tv the melter gasifier 7 in a known manner.
Thereby, the burden or sponge iron, respectively, falls from top of the meltdowngasifying zone 10 onto a flui:tized bed or a whirling bed, respectively, which is formed by the lumpy carbon carriers and is maintained by the oxygen-eont:~ining gas blown in. Due to the combustion of coke as well as, if desired, of coal under the influence of the oxygen-containing gas, so much heat is produced in the fluidized bed or in the whirling bed, respectively, that the sponge iron will melt. In the melted state, it is completely reduced by the carbon such that a pig iron melt collects on the bottom of the melter gasifier 7. A slag melt forms above the pig iron melt. These two melts are drawn off through appropriately arranged taps 11, 12 at predetermined time intervals.
During the combustion of coke and, if desired, of coal in the melter gasifier, a reducing gas essentially consisting of CO and H2 is produced, which is withdrawn from the melter gasifier 7 through supply duct 3 and is supplied to the reduction shaft furnace 1. Purification and cooling of the reducing gas formed in the melter gasifier to the temperature required for reduction is effected in a manner known per se, which, however, is not illustrated in detail in the drawing.
The top gas drawn off through the top-gas discharge duct 5 at first is subjected to pllrific~tion, for instance, in a cyclone 13 or in a scrubber in order to free it from dust particles.
Subsequently, the top gas reaches a CO2 purification means 15 by aid of a condenser 1~, in which CO2 purification means it is freed from CO2 and, at the same time, from H2S. The purification means 15 is designed as a pressure swing adsorption plant. In this case, H2O is removed, too. The thus purified top gas, through a reducing-gas supply duct 16, is fed to a second reduction shaft furnace 17 likewise operating according to the counterflow principle as the first reduction shaft furnace 1. In this shaft furnace 17 particulate ore is directly reduced.
Since the top gas has been strongly cooled in the course of purification, it is reheated prior to being introduced into the second reduction shaft furnace 17. ~eating is effected in two stages: At first, the purified top gas is subjected to indirect heating in a first stage, the heating means 18 serving this purpose being designed as a heat exchanger. The heat exchanger (recuperator) 18 is operated by means of a mixture of CO2-containing offgas separated in the C~2 purification means 15 and of puri~1ed top gas drawn off the second reduction shaft furnace 17. In addition, oxygen-cont~ining gas (oxygen being present in molecular form), such as air, is fed to the burner of the heat exchanger 18 through a duct 19. Subsequently, the heated purified top gas is subjected to afterburning in a secondary heating means 20, in which a portion of the puri~1ed top gas is burnt under oxygen supply. Thereby, the purified top gas reaches the temperature required for the reduction in the second reduction shaft furnace, which temperature ranges between 700 and 900~C.
The top gas drawn off the reduction shaft furnace 17 likewise is subjected to puri~lcation and cooling (top gas scrubber 21) in order to purify the same from dust particles CA 02206~83 1997-0~-30 and to lower its vapor content. After this, a portion of the purifie~i top gas is fed to the heat exchanger 18 through a combustion gas duct 22 running together with an offgas duct 23 discharging the C02-containing offgas from the C02 purification means. The other por~on of the top gas incurring in the second reduction shaft furnace 17 is fed to the C~2 purification means 15 via a condenser 24 through a conveying duct 25 running into the top-gas discharge duct 5, then likewise being available to the C02 removing means 15 and, after this, as a reducing gas to be recycled. The portion of the top gas of the reduction shaft furnace 17 that is not required for the process according to the invention is supplied to other purposes of use as an export gas through an export gas duct 26. A branch duct br~nehing off the offgas duct 23 also may enter into this export gas duct 26, admixing a portion of the C02-cont~ining offgas to the export gas unless required in the heat exchanger 18.
A substantial advantage of the invention is to be seen in that the combustion gas prepared by mixing C02-containing offgas and top gas from the second reduction shaft furnace 17 has a low adiabatic combustion temperature. The smoke gas temperatu~e in front of the heat exchanger bundles of the heat exchanger 18 is adjusted by the volume ratio of C02-contai~ing offgas/top gas and/or oxygen-cont:~inin~ gas. Smoke gas recycling as would be required for ~elllpeiature adjustment if only top gas were used as fuel for the heat exchanger 18 can be obviated. The smoke gas formed in the heat exchanger 18 is carried away in a purified state through a smoke-gas discharge duct 28 in a usual manner. Unless the total energy of the C02-cont~ining offgas, or of the rnixture of this offgas with top gas, respectively, is required for heating the reducing gas, it will be suitable to admix the non-required portion of the offgas or the mixture of offgas and top gas, respectively, to the export gas.
The combustion gas fed to the heating means 18 also may be formed by C02-cont~ining offgas and a heating gas, such as natural gas, etc., or by C02-containing offgas and top gas derived from the first reduction zone 4 and supplied through duct 22' illustrated in broken lines in Fig. 1.
Due to the C02-containing offgas being used in the heat exchanger 18, the energycontent of this offgas is still ~Itili7e-1. The C02-containing offgas, thus, replaces a portion of the top gas, which, in turn, may be used for other purposes. Another advantage is to be seen in that higher limiting values are permitted for the S02 formed by burning of the C02-containing offgas than are permitted for the H2S present in the unburnt C02-containing offgas.
Therefore, the use of such C02-containing offgas is feasible without being harmful to the environment. If the S02-content is still too high, smoke gas desulfurization according to the prior art is recommended. However, the components CO, H2 and CH4 have been completely converted to such an extent that any possible residual content will lie far below the permissible limiting values.
According to the exemplary embodiment explained in more detail by way of Tables 1 to 4 below, the C02-cont~ining offgas incurring in C02 purification is mixed with top gas derived from the second reduction zone 27.
In Table 1 below, the chemical composition of the C02-containing offgas formed in the C~2 purification of the top gas incurring in the ~1rst reduction zone 4 is represented.
Table 1 CO 1 1.8 % vol.
C~2 80.3 % vol.
H2 l.S % vol.
H2O 5.3 % vol.
N2 0.7 % vol.
CH4 0.4 % vol.
H2S max. 0.03 % vol.
k.T~Nm3 1 ,795 Table 2 depicts the chemical composition of tne purified and cooled top gas derived from the second reduction zone 27 of the second reduction shaft furnace 17 before being mixed with the CO2-cont~ining offgas.
Table 2 CO 43.2 %vol.
C~2 25.4 % vol.
H2 18.0 % vol.
H2O 5.7 % vol.
N2 6.2 % vol.
CH4 1.5 % vol.
H2S max. 0.00 % vol.
k.T/Nm3 1,945 Table 3 in(licat~s the chemical composition of the mixture of top gas and CO2-containing offgas, which is burnt in the heat exchanger 18.
Table 3 CO 16.6 % vol.
C~2 72.0 % vol.
H2 4.0 % vol.
H2O 5.3 % vol.
N2 1.5 % vol.
CH4 0.6 % vol.
H2S max. 0.02 % vol.
W/Nm3 2,725 The chemical composition of the smoke gas formed in the heat exchanger 18 during the combustion of this gas mixture is represented in Table 4 below.
Table 4 C~2 60.1 % vol.
H2O 7.9 % vol.
CA 02206~83 1997-0~-30 ~2 0.4 % vol.
N2 31.6 % vol.
S~2 0.02 % vol.
The adiabatic combustion temperature lies at 984~C.
In Tables 5 and 6 below, an exemplary embodiment is represented, according to which the CO2-cont~ining offgas formed in the CO2 purification of the top gas incurring in the first reduction zone 4 (Table 5) merely is mixed with oxygen and burnt. Since in that case the gas fed to the heat exchanger 18 merely is comprised of CO2-containing offgas and oxygen (or an oxygen-containing gas), it may be necessary to supply ignition burners (socalled pilot burners) of the heat exchanger 18 separately with top gas, natural gas or any other combustion gas, which, however, is of no importance because of the slight amounts required therefor. This -and also the calorific value of the gas mixture for the heat exehanger 18 - i.a. depends on the operating characteristics of the CO2-purification plant, i.e., on the amount of reductants incurring to an elevated degree if no strong separation of CO2 is effected in the CO2-pllrifi~ation plant.
Table 5 CO 11.8 '70 vol.
C~2 80.3 %vol.
H2 1.5 % vol.
H2O 5.3 % vol.
N2 0.7 % vol.
CH4 0.4 % vol.
H2S max. 0.03 ~c vol.
ld/Nm3 1,795 The chernical composition of the smoke gas is indicated in Table 6.
Table 6 C~2 91.2 % vol.
H2O 7.6 % vol.
~2 0.4 % vol.
N2 0.7 % vol.
S~2 0.03 % vol.
The adiabatic combustion temperature lies at 867~C.
According to the process variant illustrated in Fig. 2, a portion of the CO2-containing offgas is supplied through an offgas duct 29 branching off the offgas duct 23, via a heat exchanger 30 in which the CO2-con~ining offgas is heated by means of the top gas leaving the second reduction shaft furnace 17, to a heating means 31 in which it is burnt under supply of oxygen of an oxygen-cont~ining gas or of air as oxygen carrier gas. In this heating means 31, steam may, for instance, be produced in a recuperative manner; the water supply is denoted by 32 and the steam discharge is denoted by 33. A portion of the CO2-containing offgas - or even CA 02206~83 1997-0~-30 the total amount of this offgas - may be fed to the heating means 31 directly through the offgas duct 29' illustrated in broken lines in Fig. 2 without being conducted through the heat exchanger 30.
According to Fig. 3, the C02-containing offgas is burnt in the hea~ng means 31', coal or ore conveyed in and off via conveying means 36 being directly heated in a preheating chamber 34 by means of the offgas formed. The cooled smoke gas is conducted away via a smoke-gas discharge duct 35.
As is apparent from ~igs. 2 and 3, the energy inherent in the C02-containing offgas may be utilized in different ways, also by combining several types of utilization, such that the utilization of energy can be realized in an optimum manner depending on the mode of operation of the reduction shaft furnaces 1 and 17 and on the use of the export gas supplied to consumers via duct 26. It is, for instance, also possible to do without heating of the reducing gas fed to the reduction shaft furnace 17 through the reducing-gas supply duct 16 if the required reducing gas temperature can be reached merely by afterburning.
With a process of this type known, for instance, from EP-B - O 010 627, from DE-C -40 37 977 and from AT-B - 376,241, the sponge iron formed by the direct reduction is smelted in a meltdown gasifying zone under supply of lumpy carbon carriers and oxygen-cont~ining gas, wherein a fluidized bed is formed in the meltdown gasifying zone from the lumpy carbon carriers and by blowing in oxygen-cont~inin~ gas, in which fl~ li7eci bed the sponge iron particles top-charged into the meltdown gasifiying zone are braked and melted. In doing so, a reducing gas containing CO and H2 is produced, which is injected into the reduction zone and reacted there.
During this reaction, a large amount of top gas incurs, which still has a considerable content of carbon monoxide and hydrogen. If utilization of this top gas is feasible in an economic manner, production costs for sponge iron and pig iron melted therefrom or steel pre-products produced therefrom will be very low.
It is known (DE-C - 40 37 977) to supply top gas escaping from the reduction zone to a further reduction zone for reducing additional iron-oxide-containing m~teri~l after having been subjected to pllrif~ tion~ The treatment of top gas, in general, is effected by initially purifying the same from solids particles in a scrubber while being strongly cooled. After this, the C02 contained in the top gas is elimin~ted, because this would impede further utilization of the top gas as a reducing gas. Various methods have been known for the purification of top gas from C02, for instance, the pressure-swing process or chemical C02-scrubbing.
According to DE-C - 40 37 977, it has been possible to utilize the energy chemically bound in the top gas to a major extent. Yet, this involves the problem of C02-containing offgas incurring in the purification of top gas, which offgas has to be disposed of in an environmentally safe manner.
This offgas, i.a., contains CO, H2, CH4 as well as H2S and, as a result, cannot be released to the environment in such state for reasons of environmental protection. For this reason, it is suited for further processing also to a limited degree only. Consequently, the sulfur compounds usually are elimin~ted from the offgas. So far, such desulfurization has been carried out by means of various methods, such as, for instance, by what is called "Strefford scrubbing"
or by catalytic oxidation on activated carbon, etc. From DE-B - 37 16 511 it is known to remove H2S from C02-containing offgas in a desulfurization reactor by aid of sponge iron. All of these methods are expensive, requiring additional materials, such as activated carbon or absorbants, which, i.a., must be stored and disposed of separately.
It is internally known to bleed off C02-con~:~ining offgas. However, such bleeding off involves the provision of combustible supporting gas as ignition and carburizing gas, since the calorific value of the C02-cont~inin~ offgas is only low.
CA 02206~83 1997-0~-30 From EP-A - O 571 358 it is known to subject top gas incurring in the direct reduction of fine ore by aid of a reducing gas formed of reformed natural gas to C02-scrubbing and to admix the thus purified top gas to fresh reducing gas obtained from natural gas by reforming and to introduce this gas mixture into the reduction zone. Again, this involves the problem of disposing of the C02-containing offgas incurring in the purification of the top gas, although this offgas, due to the production of the reducing gas from reformed natural gas, has a lower H2S-content than the offgas incurring in the top-gas purification of reducing gas obtained from lumpy carbon carriers.
The invention aims at avoiding these disadvantages and difficulties and has as its object to provide for an efficient way of uitlization of the top gas incurring in the reduction of ore, such as a direction reduction for producing sponge iron, by overcoming the difficulties involved in the prior art. In particular, CC~2-containing offgas not only is to be processed and disposed of in an environmentally safe manner, but also is to be utilized energetically to the highest degree possible. Furthermore, problems involved in the separation of H2S, which takes place simnlt~neously with the separation of C02, likewise are to be solved in anenvironmentally safe manner.
In accordance with the invention, this object is achieved with a process of the initially defined kind by the combination of the following measures:
~ that the top gas is subjected to C02 purification, ~ that C02-cont~ining offgas separated in C~2 purification is mixed with an oxygen-containing gas and is burnt, and that its thermal energy is supplied to a consumer.
According to the invention, it is feasible to completely utilize the caloric content of the C02-containing offgas even though its energy content is not very high, without thereby affecting the environment.
Preferably, the C02-cont~ining offgas is burnt at least partially while indirectly giving off heat to reducing gas, ~ whereupon particulate iron-o~ide-containing material is reduced by means of the heated reducmg gas.
A particular advantage of the invention is to be seen in that the C02-cont~ining offgas separated from the top gas of a reduction process at least for the major part again is energetically beneficial to a reduction process, which reduction process may be a reduction process in addition to the reduction process forming the top gas or is identical with the same, which means that at least a portion of the top gas purified from C02 may be recycled as a reducing gas or an admixture to the reducing gas, to the reduction process in which it has incurred as top gas (which is known, for instance, from DE-B - 37 16 511).
-CA 02206~83 1997-0~-30 According to a preferred embodiment, the C02-containing offgas separated in C02 purifi~tion additionally is mixed with a combustible gas.
Preferably, at least a portion of the top gas forming in a reduction, such as a direct reduction, of particulate iron-oxide-containing material by means of reducing gas is employed as a combustible gas. Thereby, it is feasible to ensure heating up of the reducing gas to reduction temperature without using a foreign gas (except for the supply of an 02-cont~ining gas, such as air).
Preferably, the top gas subjected to C~2 purification is formed in a first reduction zone and the top gas purified from C02, after heating, is used as a reducing gas in at least one further reduction zone for reducing further particulate iron-oxide-cont~ining material, being reacted there. Due to these measures, it is possible to utilize the reducing gas formed in a large amount from lumpy carbon carriers in a meltdown gasifying zone, for the production of amounts of sponge iron as large as possible to an optimum degree after reaction in the reduction zone, after which it still has a considerable content of carbon monoxide and hydrogen.
In doing so, top gas formed in the second reduction zone suitably at least partially is admixed as a combustible gas to C02-containing offgas separated in C02 purification and is burnt while indirectly giving off heat to the reducing gas fed to the second reduction zone.
Advantageously, the reduction or elimin~tion of C02 is effected by means of the pressure swing adsorption process. This process is particularly advantageous if top gas having only a slight pressure incurs, because the vapor consumption for chemical scrubbing will increase enorrnously at a low pressure. When producing reducing gas from reforrned natural gas, chemical scrubbing is recommended for C02 removal.
Preferably, sponge iron from the first reduction zone is smelted in a meltdown gasifying zone while supplying solid carbon carriers and oxygen-cont~ining gas, thus forming a CO- and H2-containing reducing gas to be injected into the first reduction zone and reacted there.
A plant for carrying out the process, which comprises a reduction shaft furnace for particulate iron-oxide containing material including a supply duct for reducing gas as well as a discharge duct for top gas, is characterized in that the top-gas discharge duct runs into a C02 purification means, from which a reducing-gas supply duct departs, conducting the C02-purified top gas to a reduction shaft furnace via a heating means for the C02-purified top gas, and that an offgas duct departs from the C~2 purification means, leading separated C02-cont~ining offgas to a heating means, a duct conducting an oxygen-containing gas to the heating means running into the offgas duct.
A preferred embodiment is characterized in that an offgas duct departs from the C02 purification means, conducting separated C02-containing offgas at least partially to a heating means, a combustion-gas duct conducting a combustible gas to the heating means running into the offgas duct.
CA 02206~83 1997-0~-30 To utilize for the reduction process the energy contained in the C02-containing offgas, the heating means into which the offgas duct conducting the C02-containing offgas runs advantageously is designed as an indirect heating means for heating CO2-purified top gas, the reducing-gas supply duct conducting this top gas running into the heating means.In order to render feasible the combustion of the C02-con~ining offgas without any foreign gas, the combustion-gas duct suitably departs from a reduction shaft furnace, at least partially receiving the top gas incurring in the reduction shaft furnace.
According to a preferred embodiment, two reductioll shaft furnaces are provided,which are flow-connected via the top-gas discharge duct of the first reduction shaft furnace, via the C~2 purification means and via the reducing-gas supply duct departing therefrom and leading through the heating means.
In this case, the combustion-gas duct suitably departs from the second reduction shaft furnace.
A preferred embodiment is characterized by a melter gasifier, into which a conveying duct conveying the sponge iron from the first reduction shaft furnace runs and which comprises supply ducts for oxygen-containing gases and for solid carbon carriers as well as taps for pig iron and slag and from which a supply duct for reducing gas formed in the melter gasifier departs, running into the first reduction shaft furnace.
Preferably, the gas purification means is designed as a pressure swing adsorption plant.
Suitably, an offgas duct carrying off separated C02-containing offgas runs into a heating means designed as a steam generator.
Preferably, an offgas duct carrying off separated C02-containing offgas runs into a heating means the smoke gases of which may be carried off via a smoke-gas discharge duct comprising a heat exchanger, wherein material to be heated, such as coal, ore, etc., may be directly contacted with the smoke gas in the heat exchanger.
Another preferred embodiment is characterized in that an an offgas duct carrying off separated C02-containing offgas is conducted via a heat exchanger provided in the top-gas discharge duct of a reduction shaft furnace and subsequently runs into a heating means.
In the following, the invention will be explained in more detail by way of several processes each illustrated in a block diagram in Figs. 1 to 3.
According to Figs. 1 to 3, particulate iron-oxide material, preferably lumpy iron ore, and possible fluxes are supplied to a first reduction shaft furnace 1 through a duct 2 in a known manner. Reducing gas is blown into the reduction shaft furnace through a supply duct 3, ascending in counter-flow to the descending iron ore and effecting the reduction of the charge in t'ne reduction zone 4. After having streamed through the shaft furnace 1, this gas is carried off as a top gas via a top-gas discharge duct 5.
The reduced burden, which contains iron in the form of sponge iron, gets into a melter gasifier 7 via conveying ducts preferably designed as downpipes 6. Via a duct 8, a lumpy carbon carrier, for instance, in the form of brown-coal high-temperature coke, as well as, if CA 02206~83 1997-0~-30 desired, coal, and, in addition, via a duct 9 an oxygeh-containing gas, are supplied tv the melter gasifier 7 in a known manner.
Thereby, the burden or sponge iron, respectively, falls from top of the meltdowngasifying zone 10 onto a flui:tized bed or a whirling bed, respectively, which is formed by the lumpy carbon carriers and is maintained by the oxygen-eont:~ining gas blown in. Due to the combustion of coke as well as, if desired, of coal under the influence of the oxygen-containing gas, so much heat is produced in the fluidized bed or in the whirling bed, respectively, that the sponge iron will melt. In the melted state, it is completely reduced by the carbon such that a pig iron melt collects on the bottom of the melter gasifier 7. A slag melt forms above the pig iron melt. These two melts are drawn off through appropriately arranged taps 11, 12 at predetermined time intervals.
During the combustion of coke and, if desired, of coal in the melter gasifier, a reducing gas essentially consisting of CO and H2 is produced, which is withdrawn from the melter gasifier 7 through supply duct 3 and is supplied to the reduction shaft furnace 1. Purification and cooling of the reducing gas formed in the melter gasifier to the temperature required for reduction is effected in a manner known per se, which, however, is not illustrated in detail in the drawing.
The top gas drawn off through the top-gas discharge duct 5 at first is subjected to pllrific~tion, for instance, in a cyclone 13 or in a scrubber in order to free it from dust particles.
Subsequently, the top gas reaches a CO2 purification means 15 by aid of a condenser 1~, in which CO2 purification means it is freed from CO2 and, at the same time, from H2S. The purification means 15 is designed as a pressure swing adsorption plant. In this case, H2O is removed, too. The thus purified top gas, through a reducing-gas supply duct 16, is fed to a second reduction shaft furnace 17 likewise operating according to the counterflow principle as the first reduction shaft furnace 1. In this shaft furnace 17 particulate ore is directly reduced.
Since the top gas has been strongly cooled in the course of purification, it is reheated prior to being introduced into the second reduction shaft furnace 17. ~eating is effected in two stages: At first, the purified top gas is subjected to indirect heating in a first stage, the heating means 18 serving this purpose being designed as a heat exchanger. The heat exchanger (recuperator) 18 is operated by means of a mixture of CO2-containing offgas separated in the C~2 purification means 15 and of puri~1ed top gas drawn off the second reduction shaft furnace 17. In addition, oxygen-cont~ining gas (oxygen being present in molecular form), such as air, is fed to the burner of the heat exchanger 18 through a duct 19. Subsequently, the heated purified top gas is subjected to afterburning in a secondary heating means 20, in which a portion of the puri~1ed top gas is burnt under oxygen supply. Thereby, the purified top gas reaches the temperature required for the reduction in the second reduction shaft furnace, which temperature ranges between 700 and 900~C.
The top gas drawn off the reduction shaft furnace 17 likewise is subjected to puri~lcation and cooling (top gas scrubber 21) in order to purify the same from dust particles CA 02206~83 1997-0~-30 and to lower its vapor content. After this, a portion of the purifie~i top gas is fed to the heat exchanger 18 through a combustion gas duct 22 running together with an offgas duct 23 discharging the C02-containing offgas from the C02 purification means. The other por~on of the top gas incurring in the second reduction shaft furnace 17 is fed to the C~2 purification means 15 via a condenser 24 through a conveying duct 25 running into the top-gas discharge duct 5, then likewise being available to the C02 removing means 15 and, after this, as a reducing gas to be recycled. The portion of the top gas of the reduction shaft furnace 17 that is not required for the process according to the invention is supplied to other purposes of use as an export gas through an export gas duct 26. A branch duct br~nehing off the offgas duct 23 also may enter into this export gas duct 26, admixing a portion of the C02-cont~ining offgas to the export gas unless required in the heat exchanger 18.
A substantial advantage of the invention is to be seen in that the combustion gas prepared by mixing C02-containing offgas and top gas from the second reduction shaft furnace 17 has a low adiabatic combustion temperature. The smoke gas temperatu~e in front of the heat exchanger bundles of the heat exchanger 18 is adjusted by the volume ratio of C02-contai~ing offgas/top gas and/or oxygen-cont:~inin~ gas. Smoke gas recycling as would be required for ~elllpeiature adjustment if only top gas were used as fuel for the heat exchanger 18 can be obviated. The smoke gas formed in the heat exchanger 18 is carried away in a purified state through a smoke-gas discharge duct 28 in a usual manner. Unless the total energy of the C02-cont~ining offgas, or of the rnixture of this offgas with top gas, respectively, is required for heating the reducing gas, it will be suitable to admix the non-required portion of the offgas or the mixture of offgas and top gas, respectively, to the export gas.
The combustion gas fed to the heating means 18 also may be formed by C02-cont~ining offgas and a heating gas, such as natural gas, etc., or by C02-containing offgas and top gas derived from the first reduction zone 4 and supplied through duct 22' illustrated in broken lines in Fig. 1.
Due to the C02-containing offgas being used in the heat exchanger 18, the energycontent of this offgas is still ~Itili7e-1. The C02-containing offgas, thus, replaces a portion of the top gas, which, in turn, may be used for other purposes. Another advantage is to be seen in that higher limiting values are permitted for the S02 formed by burning of the C02-containing offgas than are permitted for the H2S present in the unburnt C02-containing offgas.
Therefore, the use of such C02-containing offgas is feasible without being harmful to the environment. If the S02-content is still too high, smoke gas desulfurization according to the prior art is recommended. However, the components CO, H2 and CH4 have been completely converted to such an extent that any possible residual content will lie far below the permissible limiting values.
According to the exemplary embodiment explained in more detail by way of Tables 1 to 4 below, the C02-cont~ining offgas incurring in C02 purification is mixed with top gas derived from the second reduction zone 27.
In Table 1 below, the chemical composition of the C02-containing offgas formed in the C~2 purification of the top gas incurring in the ~1rst reduction zone 4 is represented.
Table 1 CO 1 1.8 % vol.
C~2 80.3 % vol.
H2 l.S % vol.
H2O 5.3 % vol.
N2 0.7 % vol.
CH4 0.4 % vol.
H2S max. 0.03 % vol.
k.T~Nm3 1 ,795 Table 2 depicts the chemical composition of tne purified and cooled top gas derived from the second reduction zone 27 of the second reduction shaft furnace 17 before being mixed with the CO2-cont~ining offgas.
Table 2 CO 43.2 %vol.
C~2 25.4 % vol.
H2 18.0 % vol.
H2O 5.7 % vol.
N2 6.2 % vol.
CH4 1.5 % vol.
H2S max. 0.00 % vol.
k.T/Nm3 1,945 Table 3 in(licat~s the chemical composition of the mixture of top gas and CO2-containing offgas, which is burnt in the heat exchanger 18.
Table 3 CO 16.6 % vol.
C~2 72.0 % vol.
H2 4.0 % vol.
H2O 5.3 % vol.
N2 1.5 % vol.
CH4 0.6 % vol.
H2S max. 0.02 % vol.
W/Nm3 2,725 The chemical composition of the smoke gas formed in the heat exchanger 18 during the combustion of this gas mixture is represented in Table 4 below.
Table 4 C~2 60.1 % vol.
H2O 7.9 % vol.
CA 02206~83 1997-0~-30 ~2 0.4 % vol.
N2 31.6 % vol.
S~2 0.02 % vol.
The adiabatic combustion temperature lies at 984~C.
In Tables 5 and 6 below, an exemplary embodiment is represented, according to which the CO2-cont~ining offgas formed in the CO2 purification of the top gas incurring in the first reduction zone 4 (Table 5) merely is mixed with oxygen and burnt. Since in that case the gas fed to the heat exchanger 18 merely is comprised of CO2-containing offgas and oxygen (or an oxygen-containing gas), it may be necessary to supply ignition burners (socalled pilot burners) of the heat exchanger 18 separately with top gas, natural gas or any other combustion gas, which, however, is of no importance because of the slight amounts required therefor. This -and also the calorific value of the gas mixture for the heat exehanger 18 - i.a. depends on the operating characteristics of the CO2-purification plant, i.e., on the amount of reductants incurring to an elevated degree if no strong separation of CO2 is effected in the CO2-pllrifi~ation plant.
Table 5 CO 11.8 '70 vol.
C~2 80.3 %vol.
H2 1.5 % vol.
H2O 5.3 % vol.
N2 0.7 % vol.
CH4 0.4 % vol.
H2S max. 0.03 ~c vol.
ld/Nm3 1,795 The chernical composition of the smoke gas is indicated in Table 6.
Table 6 C~2 91.2 % vol.
H2O 7.6 % vol.
~2 0.4 % vol.
N2 0.7 % vol.
S~2 0.03 % vol.
The adiabatic combustion temperature lies at 867~C.
According to the process variant illustrated in Fig. 2, a portion of the CO2-containing offgas is supplied through an offgas duct 29 branching off the offgas duct 23, via a heat exchanger 30 in which the CO2-con~ining offgas is heated by means of the top gas leaving the second reduction shaft furnace 17, to a heating means 31 in which it is burnt under supply of oxygen of an oxygen-cont~ining gas or of air as oxygen carrier gas. In this heating means 31, steam may, for instance, be produced in a recuperative manner; the water supply is denoted by 32 and the steam discharge is denoted by 33. A portion of the CO2-containing offgas - or even CA 02206~83 1997-0~-30 the total amount of this offgas - may be fed to the heating means 31 directly through the offgas duct 29' illustrated in broken lines in Fig. 2 without being conducted through the heat exchanger 30.
According to Fig. 3, the C02-containing offgas is burnt in the hea~ng means 31', coal or ore conveyed in and off via conveying means 36 being directly heated in a preheating chamber 34 by means of the offgas formed. The cooled smoke gas is conducted away via a smoke-gas discharge duct 35.
As is apparent from ~igs. 2 and 3, the energy inherent in the C02-containing offgas may be utilized in different ways, also by combining several types of utilization, such that the utilization of energy can be realized in an optimum manner depending on the mode of operation of the reduction shaft furnaces 1 and 17 and on the use of the export gas supplied to consumers via duct 26. It is, for instance, also possible to do without heating of the reducing gas fed to the reduction shaft furnace 17 through the reducing-gas supply duct 16 if the required reducing gas temperature can be reached merely by afterburning.
Claims (19)
1. A process for producing sponge iron from particulate iron-oxide-containing material, wherein the iron-oxide-containing material in a reduction zone (4) is reduced to sponge iron by means of reducing gas and the gas forming during reduction is withdrawn as top gas, characterized by the combination of the following measures:
~ that the top gas is subjected to CO2 purification, ~ that CO2-containing offgas separated in CO2 purification is mixed with an oxygen-containing gas and . is burnt, and ~ that its thermal energy is supplied to a consumer.
~ that the top gas is subjected to CO2 purification, ~ that CO2-containing offgas separated in CO2 purification is mixed with an oxygen-containing gas and . is burnt, and ~ that its thermal energy is supplied to a consumer.
2. A process according to claim 1, characterized in that ~ the CO2-containing offgas is burnt at least partially while indirectly giving off heat to reducing gas, ~ whereupon particulate iron-oxide-containing material is reduced by means of the heated reducing gas.
3. A process according to claim 1, characterized in that the CO2-containing offgas separated in CO2 purification additionally is mixed with a combustible gas.
4. A process according to one or several of claims 1 to 3, characterized in that at least a portion of the top gas forming in a reduction, such as a direct reduction, of particulate iron-oxide-containing material by means of reducing gas is employed as a combustible gas.
5. A process according to one or several of claims 2 to 4, characterized in that the top gas subjected to CO2 purification is formed in a first reduction zone (4) and the top gas purified from CO2, after heating, is used as a reducing gas in at least one further reduction zone (27) for reducing further particulate iron-oxide-containing material, being reacted there.
6. A process according to claim 5, characterized in that top gas formed in the second reduction zone (27) at least partially is admixed as a combustible gas to CO2-containing offgas separated in CO2 purification and is burnt while indirectly giving off heat to the reducing gas fed to the second reduction zone (27).
7. A process according to one or several of claims 1 to 6, characterized in that CO2 purification of the top gas is effected by pressure swing adsorption.
8. A process according to one or several of claims 5 to 7, characterized in that sponge iron formed in the first reduction zone (4) is smelted in a meltdown gasifying zone (10) while supplying solid carbon carriers and oxygen-containing gas, thus forming a CO- and H2-containing reducing gas to be injected into the first reduction zone (4) and reacted there.
9. A plant for carrying out the process according to one or several of claims 1 to 7, comprising a reduction shaft furnace (1) for particulate iron-oxide containing material including a supply duct (3) for reducing gas as well as a discharge duct (5) for top gas, characterized in that the top-gas discharge duct (5) runs into a CO2 purification means (15), from which a reducing-gas supply duct (16) departs, conducting the CO2-purified top gas to a reduction shaft furnace (17) via a heating means (18, 20) for the CO2-purified top gas, and that an offgas duct (23, 29, 29') departs from the CO2 purification means (15), leading separated CO2-containing offgas to a heating means (18, 31), a duct (19, 19') conducting an oxygen-containing gas to the heating means (18, 31) running into the offgas duct.
10. A plant according to claim 9, characterized in that an offgas duct (23) departs from the CO2 purification means (15), conducting separated CO2-containing offgas at least partially to a heating means (18), a combustion-gas duct (22) conducting a combustible gas to the heating means (18) running into the offgas duct.
11. A plant according to claim 9 or 10, characterized in that the heating means (18) into which the offgas duct (23) conducting the CO2-containing offgas runs is designed as an indirect heating means (18) for heating CO2-purified top gas, the reducing-gas supply duct (16) conducting this top gas running into the heating means (18).
12. A plant according to claim 10 or 11, characterized in that the combustion-gas duct (22) departs from a reduction shaft furnace (17), at least partially receiving the top gas incurring in the reduction shaft furnace (17).
13. A plant according to one or several of claims 9 to 12, characterized in that two reduction shaft furnaces (1, 17) are provided, which are flow-connected via the top-gas discharge duct (5) of the first reduction shaft furnace (1), via the CO2 purification means (15) and via the reducing-gas supply duct (16) departing therefrom and leading through the heating means (18).
14. A plant according to claim 13, characterized in that the combustion-gas duct (22) departs from the second reduction shaft furnace (17).
15. A plant according to claim 14, characterized by a melter gasifier (7), into which a conveying duct (6) conveying the sponge iron from the first reduction shaft furnace runs and which comprises supply ducts (8, 9) for oxygen-containing gases and for solid carbon carriers as well as taps (11, 12) for pig iron and slag and from which a supply duct (3) for reducing gas formed in the melter gasifier (7) departs, running into the first reduction shaft furnace (1).
16. A plant according to one or several of claims 9 to 15, characterized in that the gas purification means (15) is designed as a pressure swing adsorption plant.
17. A plant according to one or several of claims 9 to 16, characterized in that an offgas duct (29, 29') carrying off separated CO2-containing offgas runs into a heating means (31) designed as a steam generator (Fig. 2).
18. A plant according to one or several of claims 9 to 17, characterized in that an offgas duct (29, 29') carrying off separated CO2-containing offgas runs into a heating means (31') the smoke gases of which may be carried off via a smoke-gas discharge duct (35) comprising a heat exchanger (34), wherein material to be heated, such as coal, ore, etc., may be directly contacted with the smoke gas in the heat exchanger (34)(Fig. 3).
19. A plant according to one or several of claims 9 to 18, characterized in that an offgas duct (29) carrying off separated CO2-containing offgas is conducted via a heat exchanger (30) provided in the top-gas discharge duct of a reduction shaft furnace (17) and subsequently runs into a heating means (31)(Figs. 2, 3).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0223294A AT405187B (en) | 1994-12-01 | 1994-12-01 | METHOD FOR THE PRODUCTION OF IRON SPONGE AND SYSTEM FOR IMPLEMENTING THE METHOD |
ATA2232/94 | 1994-12-01 |
Publications (1)
Publication Number | Publication Date |
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CA2206583A1 true CA2206583A1 (en) | 1996-06-06 |
Family
ID=3530485
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002206583A Abandoned CA2206583A1 (en) | 1994-12-01 | 1995-11-28 | Process for producing sponge iron and plant for carrying out the process |
Country Status (17)
Country | Link |
---|---|
US (1) | US5997609A (en) |
EP (1) | EP0796349B1 (en) |
JP (1) | JP3441464B2 (en) |
KR (1) | KR100247451B1 (en) |
CN (1) | CN1042955C (en) |
AT (2) | AT405187B (en) |
AU (1) | AU701539B2 (en) |
BR (1) | BR9509844A (en) |
CA (1) | CA2206583A1 (en) |
CZ (1) | CZ284766B6 (en) |
DE (1) | DE59504170D1 (en) |
RU (1) | RU2127319C1 (en) |
SK (1) | SK282341B6 (en) |
TW (1) | TW290589B (en) |
UA (1) | UA32602C2 (en) |
WO (1) | WO1996017089A1 (en) |
ZA (1) | ZA9510168B (en) |
Families Citing this family (12)
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US5582029A (en) * | 1995-10-04 | 1996-12-10 | Air Products And Chemicals, Inc. | Use of nitrogen from an air separation plant in carbon dioxide removal from a feed gas to a further process |
AT406381B (en) * | 1996-03-05 | 2000-04-25 | Voest Alpine Ind Anlagen | SYSTEM AND METHOD FOR PRODUCING METAL SPONGE |
US6478841B1 (en) | 2001-09-12 | 2002-11-12 | Techint Technologies Inc. | Integrated mini-mill for iron and steel making |
US20050151307A1 (en) * | 2003-09-30 | 2005-07-14 | Ricardo Viramontes-Brown | Method and apparatus for producing molten iron |
CN101397597B (en) * | 2007-09-26 | 2010-12-01 | 宝山钢铁股份有限公司 | Method for producing spongy iron by direct reduction of dry coal powder gasification and hot coal gas fine ore fluidized bed |
AT507823B1 (en) * | 2009-01-30 | 2011-01-15 | Siemens Vai Metals Tech Gmbh | METHOD AND APPARATUS FOR PRODUCING RAW IRONS OR LIQUID STEEL PREPARED PRODUCTS |
WO2011001288A2 (en) | 2009-06-29 | 2011-01-06 | Bairong Li | Metal reduction processes, metallurgical processes and products and apparatus |
IT1402250B1 (en) | 2010-09-29 | 2013-08-28 | Danieli Off Mecc | PROCEDURE AND EQUIPMENT FOR THE PRODUCTION OF DIRECT REDUCTION IRON USING A REDUCING GAS SOURCE INCLUDING HYDROGEN AND CARBON MONOXIDE |
DE102011077819A1 (en) * | 2011-06-20 | 2012-12-20 | Siemens Aktiengesellschaft | Carbon dioxide reduction in steelworks |
CN113249536A (en) | 2013-07-22 | 2021-08-13 | 沙特基础工业公司 | Use of top gas in direct reduction process |
CN111575428B (en) * | 2020-06-11 | 2023-05-09 | 武汉科思瑞迪科技有限公司 | Gas-solid reduction shaft furnace and method for producing sponge iron |
CN111534659B (en) * | 2020-06-11 | 2023-04-28 | 武汉科思瑞迪科技有限公司 | Parallel heat accumulating type gas-based shaft furnace and method for producing direct reduced iron |
Family Cites Families (20)
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DE252202C (en) * | ||||
US1800856A (en) * | 1926-04-07 | 1931-04-14 | Bradley Linn | Treating iron ore |
GB799551A (en) * | 1956-02-06 | 1958-08-13 | Texaco Development Corp | Reduction of a metal oxide with carbon monoxide and hydrogen |
US3653874A (en) * | 1970-01-02 | 1972-04-04 | Koppers Co Inc | Production of metal pellets from metallic oxides |
JPS5362718A (en) * | 1976-11-18 | 1978-06-05 | Nippon Steel Corp | Manufacture of reduced iron |
DE2843303C2 (en) * | 1978-10-04 | 1982-12-16 | Korf-Stahl Ag, 7570 Baden-Baden | Process and plant for the production of liquid pig iron and reducing gas in a melter gasifier |
JPS59107009A (en) * | 1982-12-11 | 1984-06-21 | Nisshin Steel Co Ltd | Method for operating blast furnace at high productivity coefficient in all-coke operation |
AT376241B (en) * | 1983-01-03 | 1984-10-25 | Voest Alpine Ag | METHOD FOR MELTING AT LEAST PARTLY REDUCED IRON ORE |
JPH0638132B2 (en) * | 1984-06-25 | 1994-05-18 | キヤノン株式会社 | Projection lens |
JPS6199613A (en) * | 1984-10-22 | 1986-05-17 | Nippon Steel Corp | Gas recirculating device for direct reduction furnace |
US4685964A (en) * | 1985-10-03 | 1987-08-11 | Midrex International B.V. Rotterdam | Method and apparatus for producing molten iron using coal |
DE3626027A1 (en) * | 1986-08-01 | 1988-02-11 | Metallgesellschaft Ag | METHOD FOR REDUCING FINE-GRAIN, IRON-CONTAINING MATERIALS WITH SOLID CARBONATED REDUCING AGENTS |
AT387038B (en) * | 1986-11-25 | 1988-11-25 | Voest Alpine Ag | METHOD AND SYSTEM FOR RECOVERING ELECTRICAL ENERGY IN ADDITION TO THE PRODUCTION OF LIQUID PIPE IRON |
DE3716511A1 (en) * | 1987-05-16 | 1988-12-01 | Voest Alpine Ag | METHOD FOR REMOVING SULFUR FROM THE EXHAUST GAS FROM A REDUCTION TUBE |
AT394201B (en) * | 1989-02-16 | 1992-02-25 | Voest Alpine Ind Anlagen | METHOD FOR GENERATING COMBUSTIBLE GASES IN A MELT-UP CARBURETTOR |
DE4037977A1 (en) * | 1990-11-29 | 1992-06-11 | Voest Alpine Ind Anlagen | METHOD FOR THE PRODUCTION OF RAW IRON OR IRON SPONGE |
AT396255B (en) * | 1991-09-19 | 1993-07-26 | Voest Alpine Ind Anlagen | Plant and process for producing pig iron and iron sponge |
AT402937B (en) * | 1992-05-22 | 1997-09-25 | Voest Alpine Ind Anlagen | METHOD AND SYSTEM FOR DIRECTLY REDUCING PARTICULATE IRON OXIDE MATERIAL |
JPH06287001A (en) * | 1993-03-31 | 1994-10-11 | Nippon Sanso Kk | Production of hydrogen and carbon dioxide |
US5676732A (en) * | 1995-09-15 | 1997-10-14 | Hylsa, S.A. De C.V. | Method for producing direct reduced iron utilizing a reducing gas with a high content of carbon monoxide |
-
1994
- 1994-12-01 AT AT0223294A patent/AT405187B/en not_active IP Right Cessation
-
1995
- 1995-01-14 TW TW084100355A patent/TW290589B/zh active
- 1995-11-28 JP JP51790096A patent/JP3441464B2/en not_active Expired - Fee Related
- 1995-11-28 RU RU97111041A patent/RU2127319C1/en not_active IP Right Cessation
- 1995-11-28 DE DE59504170T patent/DE59504170D1/en not_active Expired - Lifetime
- 1995-11-28 WO PCT/AT1995/000232 patent/WO1996017089A1/en active IP Right Grant
- 1995-11-28 US US08/849,227 patent/US5997609A/en not_active Expired - Lifetime
- 1995-11-28 CA CA002206583A patent/CA2206583A1/en not_active Abandoned
- 1995-11-28 AU AU38634/95A patent/AU701539B2/en not_active Ceased
- 1995-11-28 UA UA97052551A patent/UA32602C2/en unknown
- 1995-11-28 SK SK683-97A patent/SK282341B6/en unknown
- 1995-11-28 CN CN95196525A patent/CN1042955C/en not_active Expired - Lifetime
- 1995-11-28 EP EP95937714A patent/EP0796349B1/en not_active Expired - Lifetime
- 1995-11-28 BR BR9509844A patent/BR9509844A/en not_active IP Right Cessation
- 1995-11-28 KR KR1019970703593A patent/KR100247451B1/en not_active IP Right Cessation
- 1995-11-28 CZ CZ971629A patent/CZ284766B6/en not_active IP Right Cessation
- 1995-11-28 AT AT95937714T patent/ATE173026T1/en active
- 1995-11-30 ZA ZA9510168A patent/ZA9510168B/en unknown
Also Published As
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ATA223294A (en) | 1998-10-15 |
CN1167506A (en) | 1997-12-10 |
SK68397A3 (en) | 1998-04-08 |
TW290589B (en) | 1996-11-11 |
CZ162997A3 (en) | 1997-10-15 |
KR100247451B1 (en) | 2000-04-01 |
AU701539B2 (en) | 1999-01-28 |
ZA9510168B (en) | 1996-06-07 |
CZ284766B6 (en) | 1999-02-17 |
JP3441464B2 (en) | 2003-09-02 |
WO1996017089A1 (en) | 1996-06-06 |
ATE173026T1 (en) | 1998-11-15 |
EP0796349A1 (en) | 1997-09-24 |
US5997609A (en) | 1999-12-07 |
EP0796349B1 (en) | 1998-11-04 |
BR9509844A (en) | 1997-12-30 |
DE59504170D1 (en) | 1998-12-10 |
UA32602C2 (en) | 2001-02-15 |
JP2001511846A (en) | 2001-08-14 |
AT405187B (en) | 1999-06-25 |
SK282341B6 (en) | 2002-01-07 |
RU2127319C1 (en) | 1999-03-10 |
CN1042955C (en) | 1999-04-14 |
AU3863495A (en) | 1996-06-19 |
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